EP1104751A1 - Method for producing a dinitronaphthalene-isomer mixture having an increased 1,5-dinitronaphthalene proportion - Google Patents
Method for producing a dinitronaphthalene-isomer mixture having an increased 1,5-dinitronaphthalene proportion Download PDFInfo
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- EP1104751A1 EP1104751A1 EP00125282A EP00125282A EP1104751A1 EP 1104751 A1 EP1104751 A1 EP 1104751A1 EP 00125282 A EP00125282 A EP 00125282A EP 00125282 A EP00125282 A EP 00125282A EP 1104751 A1 EP1104751 A1 EP 1104751A1
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- dinitronaphthalene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/08—Preparation of nitro compounds by substitution of hydrogen atoms by nitro groups
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- the invention relates to the production of a dinitronaphthalene isomer mixture with an increased proportion of 1,5-dinitronaphthalene by direct nitration of Naphthalene.
- 1,5-dinitronaphthalene is a key compound for manufacturing of 1,5-diaminonaphthalene. Among other things, this is the starting compound for production of 1,5-diisocyanatonaphthalene (trade name: Desmodur 15®). 1,5-diisocyanatonaphthalene is used as an isocyanate component in polyurethane production.
- the nitration of naphthalene in mixed acid yields at elevated temperatures of 80 to 100 ° C a mixture of different dinitronaphthalenes.
- This mixture exists mainly from 1,5- and 1,8-dinitronaphthalene in a ratio of about 1 to 2.
- the mixture contains about 5% other isomers, for example 1,6-and 1,7-dinitronaphthalene.
- the unfavorable selectivity of the reaction that in the production of 1,5-dinitronaphthalene preferably a high and undesirable Proportion of 1,8-dinitronaphthalene arises.
- WO 99/12887 describes a process, also starting from 1-nitronaphthalene for the preparation of a dinitronaphthalene isomer mixture with an increased proportion of 1,5-dinitronaphthalene.
- the conversion of the nitronaphthalene takes place with nitric acid in the presence of a solid, perfluorinated, strongly acidic ion exchanger instead of.
- this method has the disadvantage that the resultant Dinitronaphthalene isomer mixture by extraction with dioxane at 90 ° C from Catalyst must be separated. The dioxane must then pass through a additional distillation step can be removed.
- DE-OS 24 53 529 describes the production of dinitronaphthalenes starting from naphthalene by nitration with nitric acid in organic solvents, for example dichloroethane, and azeotropic removal of the water of reaction. With In this process, dinitronaphthalene is obtained in high yields, but without to influence the isomer ratio.
- WO 94/19310 describes nitrations of nitroaromatics on partially with heavy metal doped Aluminum silicates, so-called claycops, as a solid catalyst, the high yields of dinitrated products with small amounts of trinitroaromatics deliver. Nitration of naphthalene by this method however, provide isomer ratios as in classic nitrations with mixed acid.
- the object was therefore a process for the preparation of a dinitronaphthalene isomer mixture to provide by nitriding naphthalene, in which simultaneous high sales and a low proportion of by-products a mixture of 1,5- and 1,8-dinitronaphthalene, which has an increased proportion of 1,5-isomer contains.
- the invention thus relates to a process for the preparation of a dinitronaphthalene isomer mixture with an increased proportion of 1,5-dinitronaphthalene Nitration of naphthalene with a molar excess of nitric acid, which characterized in that the nitration in the presence of at least one ionic liquid is carried out.
- the dinitronaphthalene isomer mixtures prepared according to the invention contain in addition to 1,8-dinitronaphthalene, a surprisingly high proportion of 1,5-dinitronaphthalene.
- the 1,5-dinitronaphthalene content is preferably above 30% by weight, based on sales, particularly preferably between 35 and 40 wt .-%.
- the By-product content, especially 1,6- and 1,7-dinitronaphthalene and higher nitrated products is low.
- nitric acid is preferably 1 to 22 times molar excess, particularly preferably in a 2 to 20-fold molar Excess, very particularly preferably in a 4 to 16-fold molar excess, based on the nitro groups to be introduced into naphthalene.
- the concentration of the nitric acid used in the process according to the invention is preferably between 50 and 100%, particularly preferably between 60 and 100%, very particularly preferably between 67 and 98%.
- the Nitric acid used in a mixture with sulfuric acid and / or phosphoric acid become.
- sulfuric acid lies Concentration preferably between 90 and 100%, particularly preferably between 96 and 100% and very particularly preferably between 98 and 100%.
- concentration lies preferably between 50 to 99%, particularly preferably between 65 to 99% and very preferably between 85 and 99%.
- this mixture is preferably from 1 to 20 parts of nitric acid and 1 part of sulfuric acid and / or phosphoric acid, particularly preferably from 1 to 10 parts of nitric acid and 1 part of sulfuric acid and / or phosphoric acid, very particularly preferably from 1 to 5 parts Nitric acid and 1 part sulfuric acid and / or phosphoric acid.
- the ionic liquids used in the process according to the invention are liquid salts of the formula Q + A - which are preferably liquid at temperatures below 90 ° C., in particular at temperatures below 80 ° C. and particularly preferably at temperatures below 50 ° C. Form salts.
- Q + A - Q + preferably represents a quaternary ammonium and / or phosphonium ion.
- Q + is particularly preferably an ammonium and / or phosphonium ion which is derived from a nitrogen and / or phosphorus-containing heterocycle which has 1, 2 or 3 nitrogen and / or phosphorus atoms and corresponds to the following general formulas in which the ring consists of 4 to 10, preferably 5 to 6 atoms and R 1 and R 2 have the meaning given above.
- R 1 to R 4 are methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, amyl, methylene, ethylidene, phenyl or benzyl
- preferred examples of R 5 are methylene, ethylene, propylene or phenylene.
- Q + is N-butylpyridinium, N-ethylpyridinium, 3-butyl-1-methylimidazolium, diethylpyrazolium, 3-ethyl-1-methylimidazolium, pyridinium, tetramethylphenylammonium and tetrabutylphosphonium.
- Q + stands for 3-butyl-1-methylimidazolium, N-butylpyridinium and N-methylpyridinium.
- a - A - preferably represents hexafluorophosphate, hexafluoroantimonate, hexafluoroarsenate, fluorosulfonate, tetrafluoroborate, nitrate, alkyl sulfonate or hydrogen sulfate.
- Very particularly preferred compounds Q + A - are 3-butyl-1-methylimidazolium tetrafluoroborate, 3-butyl-1-methylimidazolium methyl sulfonate, 3-butyl-1-methylimidazolium propyl sulfonate, N-butyl pyridinium methyl sulfonate and N-methyl pyridinium hydrogen sulfonate.
- an ionic liquid or mixtures different ionic liquids preferably in a 1 to 10 times molar Excess, particularly preferably in a 2 to 6-fold molar excess, entirely particularly preferably in a 2 to 5-fold molar excess, based on Naphthalene.
- the process according to the invention can usually be carried out at temperatures from 50 to 110 ° C, preferably at temperatures from 60 to 100 ° C and particularly preferred be carried out at temperatures of 80 to 100 ° C.
- the process according to the invention can be carried out in one without an additional solvent Mixture of at least one ionic liquid and nitric acid, if appropriate in the presence of sulfuric acid and / or phosphoric acid become.
- the method according to the invention can also be carried out after adding a solvent.
- Suitable solvents are, for example, all stable under the conditions of nitriding Solvent, preferably ligroin, chloroform, dichloromethane or cyclohexane.
- the process according to the invention is preferred without the addition of a solvent carried out.
- naphthalene at least an ionic liquid and the acid used mixed.
- the reaction time is usually between 30 minutes and 20 hours, preferably between 2 and 18 hours.
- the processing can be done by introducing the Reaction batch in water and subsequent extraction with organic Solvents, especially with a nitrated organic solvent, especially preferably with nitrobenzene. Used to work up the reaction mixture extracted with an organic solvent, this can by the expert known measures such as distillation are removed.
- the dinitronaphthalene isomer mixture can, for example, in a known manner by fractional crystallization into which the isomeric dinitronaphthalenes are separated.
- Such isomer separations for example with dimethylformamide or Dichloroethane as a solvent have already been described (Houben-Weyl, methods der organic chemistry, 1971, vol. 10, p. 494).
- naphthalene 64 mg were added to 1 g of 98% (w / w) nitric acid (16 mmol). and 0.5 g of N-methylpyridinium hydrogen sulfate (2.6 mmol) were added. Subsequently the mixture was stirred at 100 ° C. for 4 hours. The processing was carried out by introduction the reaction mixture in 20 ml ice water and subsequent extraction with Nitrobenzene.
- the isomer composition of the mixture was determined by gas chromatography. The values given are effective contents, the combustion factors of the two isomers were taken into account. 1.5 dinitronaphthalene 38% 1.8 dinitronaphthalene 53% Other dinitronaphthalenes 9.3% sales 100%
Abstract
Description
Die Erfindung betrifft die Herstellung eines Dinitronaphthalin-Isomerengemisches mit erhöhtem Anteil an 1,5-Dinitronaphthalin durch direkte Nitrierung von Naphthalin. 1,5-Dinitronaphthalin ist eine Schlüsselverbindung für die Herstellung von 1,5-Diaminonaphthalin. Dieses ist u.a. die Ausgangsverbindung zur Herstellung von 1,5-Diisocyanatonaphthalin (Handelsnamen: Desmodur 15®). 1,5-Diisocyanatonaphthalin wird als Isocyanatkomponente bei der Polyurethanherstellung eingesetzt.The invention relates to the production of a dinitronaphthalene isomer mixture with an increased proportion of 1,5-dinitronaphthalene by direct nitration of Naphthalene. 1,5-dinitronaphthalene is a key compound for manufacturing of 1,5-diaminonaphthalene. Among other things, this is the starting compound for production of 1,5-diisocyanatonaphthalene (trade name: Desmodur 15®). 1,5-diisocyanatonaphthalene is used as an isocyanate component in polyurethane production.
Die Herstellung von nitrierten Aromaten ist seit langem bekannt (G.A. Olah et al., Nitration: Methods and Mechanism, VCH, New York, 1989). Seit Jahrzehnten werden entsprechende Nitroaromaten durch Nitrierung mit einer Mischung aus Schwefel- und Salpetersäure (sogenannte Misch- oder Nitriersäure) technisch hergestellt.The production of nitrated aromatics has long been known (G.A. Olah et al., Nitration: Methods and Mechanism, VCH, New York, 1989). Have been for decades Corresponding nitroaromatics by nitration with a mixture of sulfur and nitric acid (so-called mixed or nitrating acid) industrially manufactured.
Die Nitrierung von Naphthalin in Mischsäure liefert bei erhöhten Temperaturen von 80 bis 100°C ein Gemisch verschiedener Dinitronaphthaline. Dieses Gemisch besteht hauptsächlich aus 1,5- und 1,8-Dinitronaphthalin im Verhältnis von etwa 1 zu 2. Darüber hinaus enthält das Gemisch etwa 5 % andere Isomere, beispielsweise 1,6-und 1,7-Dinitronaphthalin. Die ungünstige Selektivität der Reaktion führt also dazu, dass bei der Herstellung von 1,5-Dinitronaphthalin vorzugsweise ein hoher und unerwünschter Anteil an 1,8-Dinitronaphthalin entsteht.The nitration of naphthalene in mixed acid yields at elevated temperatures of 80 to 100 ° C a mixture of different dinitronaphthalenes. This mixture exists mainly from 1,5- and 1,8-dinitronaphthalene in a ratio of about 1 to 2. In addition, the mixture contains about 5% other isomers, for example 1,6-and 1,7-dinitronaphthalene. The unfavorable selectivity of the reaction that in the production of 1,5-dinitronaphthalene preferably a high and undesirable Proportion of 1,8-dinitronaphthalene arises.
In DE-OS 11 50 965 wird die Herstellung von 1,5-Dinitronaphthalin ausgehend von 1-Nitronaphthalin beschrieben. Eine Erhöhung der Selektivität zugunsten des gewünschten 1,5-Isomeren wird durch schnelles und intensives Vermischen des in Schwefelsäure gelösten 1-Nitronaphthalins mit Nitriersäure erreicht. Nachteil dieses Verfahrens ist die erhebliche Menge an Schwefelsäure und deren aufwendige und kostenintensive Aufarbeitung. Außerdem können bei diesem Verfahren erhebliche Mengen an trinitrierten Produkten entstehen, die sowohl die 1,5-Dinitronaphthalinausbeute deutlich mindern, als auch im Bezug auf die Sicherheitstechnik als kritisch anzusehen sind, insbesondere bei der im genannten Stand der Technik beschriebenen adiabatischen Reaktionsführung.In DE-OS 11 50 965 the production of 1,5-dinitronaphthalene is based on 1-nitronaphthalene described. An increase in selectivity in favor of the desired 1,5-isomer is obtained by rapidly and intensively mixing the in Sulfuric acid dissolved 1-nitronaphthalene achieved with nitrating acid. Disadvantage of this The process is the significant amount of sulfuric acid and its complex and costly refurbishment. In addition, this procedure can be significant Amounts of trinitrated products arise, both of which yield 1,5-dinitronaphthalene reduce significantly, as well as critical in terms of security technology are to be viewed, in particular in the case of the state of the art described adiabatic reaction.
In WO 99/12887 wird - ebenfalls ausgehend von 1-Nitronaphthalin - ein Verfahren zur Herstellung eines Dinitronaphthalin-Isomerengemisches mit erhöhtem Anteil an 1,5-Dinitronaphthalin beschrieben. Hierbei findet die Umsetzung des Nitronaphthalins mit Salpetersäure in Gegenwart eines festen, perfluorierten, stark sauren Ionenaustauschers statt. Generell hat dieses Verfahren den Nachteil, dass das entstandene Dinitronaphthalin-Isomerengemisch durch Extraktion mit Dioxan bei 90°C vom Katalysator abgetrennt werden muss. Das Dioxan muss anschließend durch einen zusätzlichen Destillationsschritt entfernt werden. Die besten Selektivitäten hinsichtlich des gewünschten 1,5-Isomers werden bei Zusatz von Sulfolan oder Nitromethan als Lösungsmittel erhalten. Der Umsatz der Reaktion liegt dann allerdings nur bei 31 bis 44 % und es entstehen beträchtliche Anteile anderer Dinitroisomere und trinitrierter Naphthaline, die schlechter aus dem Isomerengemisch abzutrennen sind.WO 99/12887 describes a process, also starting from 1-nitronaphthalene for the preparation of a dinitronaphthalene isomer mixture with an increased proportion of 1,5-dinitronaphthalene. Here the conversion of the nitronaphthalene takes place with nitric acid in the presence of a solid, perfluorinated, strongly acidic ion exchanger instead of. Generally, this method has the disadvantage that the resultant Dinitronaphthalene isomer mixture by extraction with dioxane at 90 ° C from Catalyst must be separated. The dioxane must then pass through a additional distillation step can be removed. The best selectivities regarding of the desired 1,5-isomer are added with the addition of sulfolane or nitromethane obtained as a solvent. The conversion of the reaction is then only 31 up to 44% and there are considerable proportions of other dinitroisomers and trinitrated Naphthalenes, which are more difficult to separate from the mixture of isomers.
DE-OS 24 53 529 beschreibt ausgehend von Naphthalin die Herstellung von Dinitronaphthalinen durch Nitrierung mit Salpetersäure in organischen Lösungsmitteln, beispielsweise Dichlorethan, und azeotroper Entfernung des Reaktionswassers. Mit diesem Verfahren wird Dinitronaphthalin in hohen Ausbeuten erhalten, ohne jedoch das Isomerenverhältnis zu beeinflussen.DE-OS 24 53 529 describes the production of dinitronaphthalenes starting from naphthalene by nitration with nitric acid in organic solvents, for example dichloroethane, and azeotropic removal of the water of reaction. With In this process, dinitronaphthalene is obtained in high yields, but without to influence the isomer ratio.
WO 94/19310 beschreibt Nitrierungen von Nitroaromaten an mit teilweise Schwermetall-dotierten Aluminiumsilikaten, sogenannten Claycops, als festen Katalysator, die hohe Ausbeuten an dinitrierten Produkten bei geringen Mengen an Trinitroaromaten liefern. Nach diesem Verfahren durchgeführte Nitrierungen von Naphthalin liefern allerdings Isomerenverhältnisse wie bei klassischen Nitrierungen mit Mischsäure. WO 94/19310 describes nitrations of nitroaromatics on partially with heavy metal doped Aluminum silicates, so-called claycops, as a solid catalyst, the high yields of dinitrated products with small amounts of trinitroaromatics deliver. Nitration of naphthalene by this method however, provide isomer ratios as in classic nitrations with mixed acid.
Es bestand daher die Aufgabe, ein Verfahren zur Herstellung eines Dinitronaphthalin-Isomerengemisches durch Nitrierung von Naphthalin bereitzustellen, bei dem bei gleichzeitigem hohen Umsatz und geringem Anteil an Nebenprodukten ein Gemisch von 1,5- und 1,8-Dinitronaphthalin entsteht, welches einen erhöhten Anteil an 1,5-Isomer enthält.The object was therefore a process for the preparation of a dinitronaphthalene isomer mixture to provide by nitriding naphthalene, in which simultaneous high sales and a low proportion of by-products a mixture of 1,5- and 1,8-dinitronaphthalene, which has an increased proportion of 1,5-isomer contains.
Überraschenderweise wurde nun gefunden, dass die Gegenwart von ionischen Flüssigkeiten bei der Nitrierung von Naphthalin in einem Überschuss an Salpetersäure oder Salpetersäure und Schwefelsäure und/oder Phosphorsäure eine Verschiebung des Isomerenverhältnisses hin zum 1,5-Dinitronaphthalin möglich ist.Surprisingly, it has now been found that the presence of ionic Liquids in the nitration of naphthalene in excess nitric acid or nitric acid and sulfuric acid and / or phosphoric acid a shift the isomer ratio to 1,5-dinitronaphthalene is possible.
Gegenstand der Erfindung ist somit ein Verfahren zur Herstellung eines Dinitronaphthalin-Isomerengemisches mit erhöhtem Anteil an 1,5-Dinitronaphthalin durch Nitrierung von Naphthalin mit einem molaren Überschuss an Salpetersäure, welches dadurch gekennzeichnet ist, dass die Nitrierung in Gegenwart mindestens einer ionischen Flüssigkeit durchgeführt wird.The invention thus relates to a process for the preparation of a dinitronaphthalene isomer mixture with an increased proportion of 1,5-dinitronaphthalene Nitration of naphthalene with a molar excess of nitric acid, which characterized in that the nitration in the presence of at least one ionic liquid is carried out.
Die erfindungsgemäß hergestellten Dinitronaphthalin-Isomerengemische enthalten neben 1,8-Dinitronaphthalin einen überraschend hohen Anteil an 1,5-Dinitronaphthalin. Bevorzugt liegt der Gehalt an 1,5-Dinitronaphthalin über 30 Gew.-%, bezogen auf den Umsatz, insbesondere bevorzugt zwischen 35 und 40 Gew.-%. Der Gehalt an Nebenprodukten, insbesondere 1,6- und 1,7-Dinitronaphthalin und höher nitrierten Produkten ist gering.The dinitronaphthalene isomer mixtures prepared according to the invention contain in addition to 1,8-dinitronaphthalene, a surprisingly high proportion of 1,5-dinitronaphthalene. The 1,5-dinitronaphthalene content is preferably above 30% by weight, based on sales, particularly preferably between 35 and 40 wt .-%. The By-product content, especially 1,6- and 1,7-dinitronaphthalene and higher nitrated products is low.
Im erfindungsgemäßen Verfahren wird Salpetersäure bevorzugt in einem 1 bis 22-fachen molaren Überschuss, besonders bevorzugt in einem 2 bis 20-fachen molaren Überschuss, ganz besonders bevorzugt in einem 4 bis 16-fachen molaren Überschuss, bezogen auf die in Naphthalin einzuführenden Nitrogruppen, eingesetzt. In the process according to the invention, nitric acid is preferably 1 to 22 times molar excess, particularly preferably in a 2 to 20-fold molar Excess, very particularly preferably in a 4 to 16-fold molar excess, based on the nitro groups to be introduced into naphthalene.
Die Konzentration der im erfindungsgemäßen Verfahren eingesetzten Salpetersäure liegt bevorzugt zwischen 50 und 100 %, besonders bevorzugt zwischen 60 und 100 %, ganz besonders bevorzugt zwischen 67 und 98 %.The concentration of the nitric acid used in the process according to the invention is preferably between 50 and 100%, particularly preferably between 60 and 100%, very particularly preferably between 67 and 98%.
In einer weiteren Ausführungsform des erfindungsgemäßen Verfahrens kann die Salpetersäure in einer Mischung mit Schwefelsäure und/oder Phosphorsäure eingesetzt werden.In a further embodiment of the method according to the invention, the Nitric acid used in a mixture with sulfuric acid and / or phosphoric acid become.
Wird im erfindungsgemäßen Verfahren Schwefelsäure eingesetzt, so liegt deren Konzentration bevorzugt zwischen 90 und 100 %, besonders bevorzugt zwischen 96 und 100 % und ganz besonders bevorzugt zwischen 98 und 100 %. Wird im erfindungsgemäßen Verfahren Phosphorsäure eingesetzt, so liegt deren Konzentration bevorzugt zwischen 50 bis 99 %, besonders bevorzugt zwischen 65 bis 99 % und ganz bevorzugt zwischen 85 und 99 %.If sulfuric acid is used in the process according to the invention, the latter lies Concentration preferably between 90 and 100%, particularly preferably between 96 and 100% and very particularly preferably between 98 and 100%. Will in the invention If phosphoric acid is used, its concentration lies preferably between 50 to 99%, particularly preferably between 65 to 99% and very preferably between 85 and 99%.
Wird im erfindungsgemäßen Verfahren eine Mischung aus Salpetersäure und Schwefelsäure und/oder Phosphorsäure eingesetzt, so besteht diese Mischung bevorzugt aus 1 bis 20 Teilen Salpetersäure und 1 Teil Schwefelsäure und/oder Phosphorsäure, besonders bevorzugt aus 1 bis 10 Teilen Salpetersäure und 1 Teil Schwefelsäure und/oder Phosphorsäure, ganz besonders bevorzugt aus 1 bis 5 Teilen Salpetersäure und 1 Teil Schwefelsäure und/oder Phosphorsäure.If a mixture of nitric acid and Sulfuric acid and / or phosphoric acid used, this mixture is preferably from 1 to 20 parts of nitric acid and 1 part of sulfuric acid and / or phosphoric acid, particularly preferably from 1 to 10 parts of nitric acid and 1 part of sulfuric acid and / or phosphoric acid, very particularly preferably from 1 to 5 parts Nitric acid and 1 part sulfuric acid and / or phosphoric acid.
Bei den im erfindungsgemäßen Verfahren eingesetzten ionischen Flüssigkeiten handelt es sich um flüssige Salze der Formel Q+ A-, die bevorzugt bei Temperaturen unterhalb von 90°C, insbesondere bei Temperaturen unterhalb von 80°C und besonders bevorzugt bei Temperaturen unterhalb von 50°C flüssige Salze bilden.The ionic liquids used in the process according to the invention are liquid salts of the formula Q + A - which are preferably liquid at temperatures below 90 ° C., in particular at temperatures below 80 ° C. and particularly preferably at temperatures below 50 ° C. Form salts.
In der Formel Q+ A- steht Q+ bevorzugt für ein quarternäres Ammonium- und/oder
Phosphoniumion. Besonders bevorzugt handelt es sich bei Q+ um eine Verbindung
aus der Reihe
Besonders bevorzugt handelt es sich bei Q+ um ein Ammonium- und/oder Phosphoniumion, welches sich von einem stickstoff- und/oder phosphorhaltigen Heterocyclus ableitet, welcher 1, 2 oder 3 Stickstoff- und/oder Phosphoratome aufweist und den nachfolgenden allgemeinen Formeln entspricht in welchen der Ring aus 4 bis 10, bevorzugt 5 bis 6 Atomen besteht und R1 und R2 die oben angegebene Bedeutung besitzen.Q + is particularly preferably an ammonium and / or phosphonium ion which is derived from a nitrogen and / or phosphorus-containing heterocycle which has 1, 2 or 3 nitrogen and / or phosphorus atoms and corresponds to the following general formulas in which the ring consists of 4 to 10, preferably 5 to 6 atoms and R 1 and R 2 have the meaning given above.
Weiterhin steht Q+ bevorzugt für quarternäre Ammonium- und/oder Phosphoniumionen
aus der Reihe
Bevorzugte Beispiele für R1 bis R4 sind Methyl, Ethyl, Propyl, Isopropyl, Butyl, sek.-Butyl, tert.-Butyl, Amyl, Methylen, Ethyliden, Phenyl oder Benzyl, bevorzugte Beispiele für R5 sind Methylen, Ethylen, Propylen oder Phenylen. In einer besonders bevorzugten Ausführungsform steht Q+ für N-Butylpyridinium, N-Ethylpyridinium, 3-Butyl-1-methylimidazolium, Diethylpyrazolium, 3-Ethyl-1-methylimidazolium, Pyridinium, Tetramethylphenylammonium und Tetrabutylphosphonium. In einer ganz besonders bevorzugten Ausführungsform steht Q+ für 3-Butyl-1-methylimidazolium, N-Butylpyridinium und N-Methylpyridinium.Preferred examples of R 1 to R 4 are methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, amyl, methylene, ethylidene, phenyl or benzyl, preferred examples of R 5 are methylene, ethylene, propylene or phenylene. In a particularly preferred embodiment, Q + is N-butylpyridinium, N-ethylpyridinium, 3-butyl-1-methylimidazolium, diethylpyrazolium, 3-ethyl-1-methylimidazolium, pyridinium, tetramethylphenylammonium and tetrabutylphosphonium. In a very particularly preferred embodiment, Q + stands for 3-butyl-1-methylimidazolium, N-butylpyridinium and N-methylpyridinium.
In der Formel Q+ A- steht A- bevorzugt für Hexafluorophosphat, Hexafluoroantimonat, Hexafluoroarsenat, Fluorosulfonat, Tetrafluoroborat, Nitrat, Alkylsulfonat oder Hydrogensulfat. Besonders bevorzugt steht A- für Tetrafluoroborat, Nitrat, Methylsulfonat, Propylsulfonat oder Hydrogensulfat.In the formula Q + A - A - preferably represents hexafluorophosphate, hexafluoroantimonate, hexafluoroarsenate, fluorosulfonate, tetrafluoroborate, nitrate, alkyl sulfonate or hydrogen sulfate. A - particularly preferably stands for tetrafluoroborate, nitrate, methyl sulfonate, propyl sulfonate or hydrogen sulfate.
Ganz besonders bevorzugte Verbindungen Q+ A- sind 3-Butyl-1-methylimidazoliumtetrafluoroborat, 3-Butyl-1-methylimidazoliummethylsulfonat, 3-Butyl-1-methylimidazoliumpropylsulfonat, N-butylpyridiniummethylsulfonat und N-methylpyridiniumhydrogensulfat.Very particularly preferred compounds Q + A - are 3-butyl-1-methylimidazolium tetrafluoroborate, 3-butyl-1-methylimidazolium methyl sulfonate, 3-butyl-1-methylimidazolium propyl sulfonate, N-butyl pyridinium methyl sulfonate and N-methyl pyridinium hydrogen sulfonate.
Im erfindungsgemäßen Verfahren können auch Mischungen verschiedener ionischer Flüssigkeiten eingesetzt werden.Mixtures of different ionic ones can also be used in the process according to the invention Liquids are used.
Im erfindungsgemäßen Verfahren wird eine ionische Flüssigkeit oder Mischungen verschiedener ionischer Flüssigkeiten bevorzugt in einem 1 bis 10-fachen molaren Überschuss, besonders bevorzugt in einem 2 bis 6-fachen molaren Überschuss, ganz besonders bevorzugt in einem 2 bis 5-fachen molaren Überschuss, bezogen auf Naphthalin, eingesetzt.In the process according to the invention, an ionic liquid or mixtures different ionic liquids preferably in a 1 to 10 times molar Excess, particularly preferably in a 2 to 6-fold molar excess, entirely particularly preferably in a 2 to 5-fold molar excess, based on Naphthalene.
Üblicherweise kann das erfindungsgemäße Verfahren bei Temperaturen von 50 bis 110°C, vorzugsweise bei Temperaturen von 60 bis 100°C und besonders bevorzugt bei Temperaturen von 80 bis 100°C durchgeführt werden. The process according to the invention can usually be carried out at temperatures from 50 to 110 ° C, preferably at temperatures from 60 to 100 ° C and particularly preferred be carried out at temperatures of 80 to 100 ° C.
Das erfindungsgemäße Verfahren kann ohne zusätzliches Lösungsmittel in einem Gemisch aus mindestens einer ionischer Flüssigkeit und Salpetersäure, gegebenenfalls in Anwesenheit von Schwefelsäure und/oder Phosphorsäure, durchgeführt werden. In einer weiteren Ausführungsform kann das erfindungsgemäße Verfahren auch nach Zusatz eines Lösungsmittels durchgeführt werden. Geeignete Lösungsmittel sind beispielsweise alle unter den Bedingungen der Nitrierung stabilen Lösungsmittel, bevorzugt Ligroin, Chloroform, Dichlormethan oder Cyclohexan.The process according to the invention can be carried out in one without an additional solvent Mixture of at least one ionic liquid and nitric acid, if appropriate in the presence of sulfuric acid and / or phosphoric acid become. In a further embodiment, the method according to the invention can also be carried out after adding a solvent. Suitable solvents are, for example, all stable under the conditions of nitriding Solvent, preferably ligroin, chloroform, dichloromethane or cyclohexane.
Bevorzugt wird das erfindungsgemäße Verfahren ohne Zusatz eines Lösungsmittels durchgeführt.The process according to the invention is preferred without the addition of a solvent carried out.
Zur Durchführung des erfindungsgemäßen Verfahrens werden Naphthalin, mindestens eine ionische Flüssigkeit und die eingesetzte Säure vermischt. Um die vollständige Reaktion sicherzustellen, kann die Umsetzung unter guter Durchmischung des Reaktionsansatzes, beispielsweise durch intensives Rühren, durchgeführt werden. Die Reaktionsdauer liegt üblicherweise zwischen 30 Minuten und 20 Stunden, bevorzugt zwischen 2 und 18 Stunden. Die Aufarbeitung kann durch Einbringen des Reaktionsansatzes in Wasser und anschließender Extraktion mit organischem Lösungsmittel, bevorzugt mit einem nitrierten organischen Lösungsmittel, besonders bevorzugt mit Nitrobenzol, erfolgen. Wird zur Aufarbeitung des Reaktionsansatzes mit einem organischen Lösungsmittel extrahiert, so kann dieses durch dem Fachmann bekannte Maßnahmen wie Destillation entfernt werden.To carry out the process according to the invention, naphthalene, at least an ionic liquid and the acid used mixed. To the full Ensure reaction, the implementation with thorough mixing of the reaction batch, for example by intensive stirring. The reaction time is usually between 30 minutes and 20 hours, preferably between 2 and 18 hours. The processing can be done by introducing the Reaction batch in water and subsequent extraction with organic Solvents, especially with a nitrated organic solvent, especially preferably with nitrobenzene. Used to work up the reaction mixture extracted with an organic solvent, this can by the expert known measures such as distillation are removed.
Das Dinitronaphthalin-Isomerengemisch kann in bekannter Weise, beispielsweise durch fraktionierte Kristallisation, in die isomeren Dinitronaphthaline getrennt werden. Derartige Isomerentrennungen, beispielsweise mit Dimethylformamid oder Dichlorethan als Lösungsmittel, sind bereits beschrieben (Houben-Weyl, Methoden der organischen Chemie, 1971, Vol. 10, S. 494). The dinitronaphthalene isomer mixture can, for example, in a known manner by fractional crystallization into which the isomeric dinitronaphthalenes are separated. Such isomer separations, for example with dimethylformamide or Dichloroethane as a solvent have already been described (Houben-Weyl, methods der organic chemistry, 1971, vol. 10, p. 494).
Die folgenden Beispiele sollen die Erfindung erläutern, ohne sie jedoch in ihrem Umfang zu begrenzen. The following examples are intended to illustrate the invention without, however, its scope to limit.
Zu 1 g 98 % (w/w) Salpetersäure (16 mmol) wurden 64 mg Naphthalin (0,5 mmol) und 0,5 g N-Methylpyridiniumhydrogensulfat (2,6 mmol) gegeben. Anschließend wurde der Ansatz 4 Stunden bei 100°C gerührt. Die Aufarbeitung erfolgte durch Einbringen des Reaktionsansatzes in 20 ml Eiswasser und anschließender Extraktion mit Nitrobenzol.64 mg of naphthalene (0.5 mmol) were added to 1 g of 98% (w / w) nitric acid (16 mmol). and 0.5 g of N-methylpyridinium hydrogen sulfate (2.6 mmol) were added. Subsequently the mixture was stirred at 100 ° C. for 4 hours. The processing was carried out by introduction the reaction mixture in 20 ml ice water and subsequent extraction with Nitrobenzene.
Die Isomerenzusammensetzung des Gemisches wurde gaschromatographisch
bestimmt. Die angegebenen Werte sind effektive Gehalte, die Verbrennungsfaktoren
der beiden Isomeren wurden berücksichtigt.
Die weiteren Beispiele 2 bis 9 wurden gemäß Beispiel 1 mit den in Tabelle 1 angegebenen Parametern durchgeführt. The further examples 2 to 9 were carried out according to example 1 with the parameters given in table 1.
Claims (10)
Applications Claiming Priority (2)
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DE19958389A DE19958389A1 (en) | 1999-12-03 | 1999-12-03 | Process for the preparation of a dinitronaphthalene isomer mixture with an increased proportion of 1,5-dinitronaphthalene |
DE19958389 | 1999-12-03 |
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EP1104751A1 true EP1104751A1 (en) | 2001-06-06 |
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EP00125282A Withdrawn EP1104751A1 (en) | 1999-12-03 | 2000-11-21 | Method for producing a dinitronaphthalene-isomer mixture having an increased 1,5-dinitronaphthalene proportion |
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US (1) | US6420616B1 (en) |
EP (1) | EP1104751A1 (en) |
JP (1) | JP2001163835A (en) |
DE (1) | DE19958389A1 (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2002030865A2 (en) | 2000-10-10 | 2002-04-18 | The Queen's University Of Belfast | Aromatic nitration reactions |
WO2003020683A1 (en) * | 2001-09-05 | 2003-03-13 | Cytec Canada Inc. | Nitration of aromatic compounds |
CN102249927A (en) * | 2010-05-20 | 2011-11-23 | 江苏大华化学工业有限公司 | Clean nitration reaction of p-chlorobenzotrifluoride under catalysis of degradable functional ionic liquid |
CN104478729A (en) * | 2014-11-24 | 2015-04-01 | 常州大学 | Method for synthesizing 1,5-dinitronaphthalene and 1,8-dinitronaphthalene by continuous flow microchannel reaction |
CN104478730A (en) * | 2014-12-31 | 2015-04-01 | 浙江永太科技股份有限公司 | 2-4-dichloronitrobenzene synthesis method utilizing micro-channel reactor |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10209644A1 (en) | 2002-03-05 | 2003-09-18 | Bayer Ag | Process for the preparation of a dinitronaphthalene isomer mixture with a high proportion of 1,5-dinitronaphthalene |
JP4239531B2 (en) * | 2002-09-04 | 2009-03-18 | 株式会社ジーエス・ユアサコーポレーション | Ionic compound, and electrolyte and electrochemical device using the same |
JP4066835B2 (en) * | 2003-02-18 | 2008-03-26 | 株式会社デンソー | Manufacturing method of laminated gas sensor element |
EP1529772B1 (en) * | 2003-11-05 | 2011-08-17 | Bayer MaterialScience AG | Process for the production of 1,5-dinitronaphthalene |
DE102004038577B4 (en) * | 2004-08-06 | 2013-03-07 | Basf Se | Preparation of 1,5-naphthalenediamine by Selective Halogenation |
JP4992869B2 (en) * | 2008-09-01 | 2012-08-08 | 株式会社Gsユアサ | Ionic compound, and electrolyte and electrochemical device using the same |
CN103265435A (en) * | 2013-06-20 | 2013-08-28 | 江苏大华化学工业有限公司 | Clean preparation method of 4-chlorine-3-nitrobenzotrifluoride |
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DE1150965B (en) * | 1961-09-22 | 1963-07-04 | Basf Ag | Process for the continuous production of 1,5 and 1,8-dinitronaphthalene |
WO2000032572A2 (en) * | 1998-12-04 | 2000-06-08 | Symyx Technologies | Combinatorial discovery and testing of ionic liquids |
WO2001009065A2 (en) * | 1999-07-29 | 2001-02-08 | Merck Patent Gmbh | Nitration in a static micromixer |
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DE2453529A1 (en) | 1974-11-12 | 1976-05-13 | Bayer Ag | PROCESS FOR THE MANUFACTURING OF NITRONAPHTHALINES |
PT101207A (en) | 1993-02-26 | 1994-08-31 | Inst Nac De Engenharia E Tecno | PROCESS FOR THE NITRACAO OF AROMATIC COMPOUNDS IN SOFT AND NON-CORROSIVE CONDITIONS |
DE19739202C1 (en) * | 1997-09-08 | 1999-03-25 | Bayer Ag | Process for the preparation of a dinitronaphthalene isomer mixture with a high proportion of 1,5-dinitronaphthalene |
-
1999
- 1999-12-03 DE DE19958389A patent/DE19958389A1/en not_active Withdrawn
-
2000
- 2000-11-21 EP EP00125282A patent/EP1104751A1/en not_active Withdrawn
- 2000-11-22 JP JP2000355730A patent/JP2001163835A/en active Pending
- 2000-11-29 US US09/726,241 patent/US6420616B1/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1150965B (en) * | 1961-09-22 | 1963-07-04 | Basf Ag | Process for the continuous production of 1,5 and 1,8-dinitronaphthalene |
WO2000032572A2 (en) * | 1998-12-04 | 2000-06-08 | Symyx Technologies | Combinatorial discovery and testing of ionic liquids |
WO2001009065A2 (en) * | 1999-07-29 | 2001-02-08 | Merck Patent Gmbh | Nitration in a static micromixer |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2002030865A2 (en) | 2000-10-10 | 2002-04-18 | The Queen's University Of Belfast | Aromatic nitration reactions |
WO2002030865A3 (en) * | 2000-10-10 | 2003-03-13 | Univ Belfast | Aromatic nitration reactions |
US6906231B2 (en) | 2000-10-10 | 2005-06-14 | The Queen's University Of Belfast | Aromatic nitration reactions |
WO2003020683A1 (en) * | 2001-09-05 | 2003-03-13 | Cytec Canada Inc. | Nitration of aromatic compounds |
CN102249927A (en) * | 2010-05-20 | 2011-11-23 | 江苏大华化学工业有限公司 | Clean nitration reaction of p-chlorobenzotrifluoride under catalysis of degradable functional ionic liquid |
CN104478729A (en) * | 2014-11-24 | 2015-04-01 | 常州大学 | Method for synthesizing 1,5-dinitronaphthalene and 1,8-dinitronaphthalene by continuous flow microchannel reaction |
CN104478730A (en) * | 2014-12-31 | 2015-04-01 | 浙江永太科技股份有限公司 | 2-4-dichloronitrobenzene synthesis method utilizing micro-channel reactor |
CN104478730B (en) * | 2014-12-31 | 2016-06-22 | 浙江永太科技股份有限公司 | A kind of method utilizing micro passage reaction synthesis 2,4-dichloronitrobenzene |
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DE19958389A1 (en) | 2001-06-07 |
US6420616B1 (en) | 2002-07-16 |
JP2001163835A (en) | 2001-06-19 |
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